DE2124526A1 - Use detergent and cleaning agent mixtures with controlled foam - Google Patents

Description

The present invention relates to laundry detergent and cleaning agent mixtures with a regulated foam profile and in particular detergent and cleaning agent mixtures containing builders, which contain a water-soluble organic, non-cationic, surface-active agent, a builder, a foam control agent, an organic, polymer substance soluble in the washing mixture, and optionally contain a bleaching agent. In particular, relates the present invention relates to a granular or powdery High-performance detergent and cleaning agent mixture with a regulated foam profile when used at high temperatures, which are a water-soluble organic, synthetic, non-cationic, surface active agent

1098Λ9 / 1886

4 ·. tm C

• water-soluble inorganic builder, alone or in . Coordination with a water-soluble organic builder is used, a show-ground, silicon-containing Medium, a copolymer of LIaIe ins aureanhydrid and a vinyl compound and water-soluble salts thereof and optionally an inorganic hydrogen peroxide addition compound

• Contains binding as a bleach.

In many industrial and domestic work practices that use aqueous solutions the foaming is to a large extent disruptive. the most known detergent and cleaning agent mixtures are r high foaming products; when used in washing machines and automatic washing machines, they foam excessively, which results in them ■ has that thick foam overflows from the machines or automats. Reduced in Eorisontal washing machines of the circulation type excessive foam by impairing the Y / ash effect the free fall of the laundry, overflowing foam can damage the machine, as well as that from .User the amount of. Detergent is reduced so much that this is insufficient to achieve the desired cleaning.

The foam profile of aqueous 7 / ash and cleaning solutions varies depending on the temperatures and the water hardness of the aqueous solutions, the type and the concentration the surfactant, the agitation of the aqueous solution, for example according to the type of washing machine and the detergents.

It is known that the foam formation of many .known detergent and cleaning agent mixtures by the incorporation of foam suppressants, such as long-chain fatty acids, long-chain fatty alcohols, esters and / or ethers of such long-chain fatty acids and alcohols, fatty acid amines and amines, silicones, etc., in the Mixtures is regulated. All of these foam suppressors influence the properties of • maintaining the whiteness of detergents and cleaning agents

109849/1886 - 2 -

mixes negative; most are only at low temperatures, ie between O and etv / a 40 to 60 ⁰ C, effective, many are sensitive to water hardness; some cannot always be used because they interact with ash additives, while others act on dirt or are ineffective in strongly alkaline solutions. All of these disadvantages limit the use of foam-controlled detergent and cleaning agent mixtures to a very considerable extent. ".

It would therefore be advantageous to use a detergent and cleaning agent mixture to create, in which the foaming at any working temperature and especially at 'high temperatures, i.e. from about 60 ° C to the boiling point of the aqueous detergent and cleaning agent solution, regardless of whose water hardness, alkalinity and intensity of movement can be regulated or even avoided without the properties of maintaining the degree of heat and detergent mix are negatively affected. .

The aim of the present invention is therefore to create a washing and cleaning agent mixture, the foaming at any use temperature and in particular at high temperatures, ie from about 60 ⁰ C to boiling point, can be completely controlled without adversely affecting their whiteness maintenance properties. ··

According to the present invention, it has been found that the foaming or foaming of a detergent mixture which contains a non-cationic organic surface-active agent and optionally a builder. Usual detergents and cleaning agents additives and contains a hydrogen peroxide addition compound, completely without. Influencing the Tfeißgradaufrechterhaltungseigenschaften dv ~ Ii incorporating the following components, calculated on the weight of the finished product, can be regulated. (A) etv / a 0.05 weight -% to about 5 wt .-% of a suds-regulating LIittels from silicones; finely divided silanized silica

1O984Q / 1,886

-re; particulate hydrophobic polymers and copolymers of Group comprising styrene, Athens, fluoroethene, butylene and isobutylene and mixtures thereof; and

(B) from about O ₅ 5 wt -.% To about 8 wt .- $ of a polymeric compound of the polymers of a vinyl compound having the formula CHp HCM = ^1, wherein M ^{1 is} a pyrrolidone (C ₄ H ₆ ON) radical or a -OCOCH, -, -OCOC ₂ Hn-I -OCH ₇ - * -OCpHc radical and copolymers thereof with a molecular weight between 50OO and 50,000 \ Polymers of the general formula - (CH ₂ -CHp-0-) - with a molecular weight between 1000 and 50,000;

»Copolymers of maleic anhydride and a vinyl compound ρ ρ
of the formula CH ₂ = HCM, in which M denotes a C 1 -C -alkyl ether residue, preferably a methyl ether residue, a phenyl residue or a water-soluble atom, and the group comprising the "water-soluble salts thereof with a molecular weight between 10,000 and 500,000.

Preferred VTasch- and detergent mixtures contain, calculated on the basis of the weight of a finished product of: (a) about 2 ° / o to about 50% of a water soluble organic, synthetic, non-cationic surface active agent, preferably 7% to 14% of a sulfuric acid reaction product; (b) about 15 % to about 80 % of a water-soluble builder, preferably 15 % to 4-5 % of an inorganic builder, used alone or in combination with a water-soluble organic builder;

(c) from about 0.05 % to about 3 % of a foam control agent selected from the group consisting of silicones, silanized silica, and preferably mixtures of the two; (d) from about 0.5 to about 5 fi £ »f4 preferably 1.0 to 2.5 f» a

Calinic anhydride / vinyl-C ^ .- ^ lkylmthercopolyraers, preferably maleic anhydride / vinylraethylether copolyraer, and the water-soluble alkali metal salts thereof; and (e) optionally from about 12 to about 50% of a hydrogen peroxide addition compound, preferably from 25% to 35% of atrium phosphate.

109-8440 / 1886

Those contained in the deletions according to the invention Connections are described in more detail as follows:. ·

1. Non-cationic surfactants.

. (a) Natural soaps. The in. Framework of the present • Soaps that can be used in the invention are ammonium and C ,, p-alkanolammonium (e.g. triethsnolammonium) . Salts and preferably sodium and xalium salts of higher Cg_o / _ ~ naturally occurring vegetable fatty acids or animal esters, e.g. palm oil, coconut oil, tallow, fish oils, lard and their mi-. sung. . '·

(b) Non-soap anionic synthetic detergents:. ■ • A preferred class can generally be considered as water-soluble salts, particularly alkali metal salts of organic sulfuric acid reaction products are addressed, which in their molecular structure, a Alkyl radical containing 8 to 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical contain (the term alkyl includes the alkyl part of higher acyl radicals). The sodium

'. and potassium alkyl sulfates, particularly those obtained by sulfating the higher alcohols (C 1-6 carbon atoms) and sodium or potassium O-alkyl benzene sulfonates; Sodium alkyl glyceryl ether sulfonates; Sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; Sodium or potassium salts of · · 'sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (for example tallow or coconut oil alcohols) and 1 to 6 moles of ethylene oxide; Sodium or potassium salts of alkylphenolethylene oxide ether sulfate with 1 to 10 units of ethylene oxide per molecule, in which the alkyl radicals contain 8 to 12 carbon atoms; the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, as well as other products known per se. 109849/1886.

(c) Nonionic synthetic detergents: general these products are defined as compounds that result in the condensation of alkylene oxide groups (hydrophilic type) with, an organic hydrophobic compound, which is more aliphatic or alkylaroinatic Nature can be produced. Preferred classes of nonionic synthetic detergents are the following: .

1. Compounds formed by the condensation of ethylene oxide with a hydrophobic base, by. Condensation of propylene oxide with pro-

w pylene glycol arise, whereby the hydrophobic Ab

Section of the molecule has a molecular weight of about 15OO to 1800, while the polyoxyethylene content is about 50 % of the total weight of the. Condensation product is.

2. The polyethylene oxide condensates of Cc ,, Q-alkylphenols with ethylene oxide, the ethylene oxide being present in amounts which are 5 to 25 moles of ethylene oxide

per mole of alkyiphenol.

3. Nonionic synthetic detergents which ψ from the condensation of jithylencxid with the product '

Derive duct that in the .Reaction of propylene--. oxide and Äthylendiaiain is formed. For example, compounds that contain 40% by weight to 80% by weight Contain polyoxyethylene and have a molecular weight of about 5000 to about 11,000 and at ·. . . the reaction of ethylene oxide groups with a hydrophobic Base is formed, which is the reaction product of ethylenediamine and excess propylene oxide - represents, these bases having a molecular weight in the order of 2500 to 3000 exhibit, satisfactory.

4. The condensation product of aliphatic alcohol

840/1886

pick up that have 8 »to 22 carbon atoms * with ethylene oxide, e.g. a coconut alcohol-Ethy- ' lenoxide condensate with 5 to 30 moles of ethylene oxide per LIoI coconut alcohol, with the coconut alcohol fraction Has 10 to 14 carbon atoms ..

5 · The Aumoniak-, Llonoethanol- and Diethanolaadde of fatty acids with an acyl radical that has about 8 to about 18 carbon atoms. .

6. Long-chain tertiary amine oxides, according to the ' general formula

t I

wherein R ^{1 is} an alkyl radical having about 8 to about carbon atoms, R and R ^ are each methyl,

Xthyl or hydroxyethyl radicals, R is ethylene and η O or an integer up to 10. The arrow in the formula is a common representation of a seaipolar bond. Specific examples of amine oxide detergents include: dimethyldodecylamine oxide; Acetyldimethylamine oxide; bis- (2-hydroxyethyl) -dodecylamine oxides, bis- (2-hydroxyethyl) -3-dodecxy-i-hydroxypropylamine oxide.

7. Long-chain tertiary phosphine oxides, according to the general formula

⁵ R ⁶ R ⁷ P

wherein R ⁷ is an alkyl, alkenyl or monohydroxy alkyl radical _# part having 10 to 24 carbon atoms in the alkyl, and R and R 'are each alkyl or monohydroxyalkyl groups containing from 1 bis'3 carbon atoms The arrow in the formula is a conventional Daretel -.

109I4Ö / UI8

development of a semi-polar bond. Examples of suitable phosphine oxides are in the British Pa- · Publication No. 995,260 and include: dimethyldodecylphosphine oxide; Diethyldodecylphosphine oxide; and dimethyl 2-hydroxydodecylphosphine oxide. '

8. Long chain sulfoxides with the formula '

0 Λ

. . - where R is an alkyl radical with 10. to 28 carbon " material atoms, 0 to 5 ether bonds and 0 to 2

■ HydroxyIsubstituenten, where at least a portion of R is an alkyl radical that is none

• Has ether bonds and 10 to 18 carbon '

contains atoms and'worin R 'is an alkyl radical with 1 to 3 carbon atoms and 1 to 2 hydroxyl groups. Specific examples of these sulfoxides are: 3-methoxytridecylmethylsulfoxide and 3 ~ hydroxy-4- dodecoxybutyl methyl sulfoxide. . . »'. ·

(d) Ampholytes before synthetic detergents can generally as derivatives of aliphatic secondary .and

Ψ '■ tertiary amines are described, in which one of the aliphatic substituents 8 to 18 carbon atoms

. me and an anionic water-solubilizing group, e.g. Carboxy, SuIfο, SuIfato, Phosphato or

• Phosphono, contains. · Examples of compounds that '' Falling under this definition are sodium 3-dodocylaminopropionate and sodium 3-dodecylaminopropanesulfonate.

(e) Zwitterionic synthetic detergents .can generally as derivatives of aliphatic quaternary JUnaonium, Phosphonium and sulfonium compounds "wherein one of the aliphatic

containing 8 to 18 carbon atoms and An anionic, water-soluble group, e.g. B. carboxy, sulfo, sulfato, phosphato or phosphono, having. Examples of compounds that fall under this definition are 3- (N, JT-dimethyl-N-hexa ~ decylaainonio) -propane ~ 1-sulfonate and 3- (lf, N-diaothyll · T-hexadecylaπl2lonio) -2-hydroxypropane-1- ■ sulfonate, especially for their excellent cold water detergent characteristics preferred are · see, for example, British patent specification Kr. 987,795; "

2. Detergent Builders. ·

The Dötergens-Qerüststoffe useful in Hahmen the present invention are, water-soluble inorganic alkaline builder salts and organic alkaline complexing builder salts and mixtures thereof, as will be described in more detail 'below and illustrated.

Examples of water-soluble inorganic alkaline builder salts (and mixtures thereof) which can be used in the mixtures according to the invention include the sodium, Potassium, ammonium and substituted ammonium carbonates, borates, phosphates, condensed polyphosphates, bicarbonates and silicates. Specific examples of such salts are the sodium and potassium tripolyphosphates, carbonates, tetra- '· borates, pyrophosphates, orthophosphates, bicarbonates and -hexametaphosphate. .

Examples of organic alkaline builder salts (and their mixtures) which can be used are the alkali metal j ammonium or substituted ammonium aminopolycarboxylates; for example sodium and potassium N- (s-hydroxyethyl) ethylenediamine triacetate and sodium and potassium nitrilotriacetates. Other valuable polycarboxylate builders are the liatriuai and potassium salts of. Polynaleic acid, polyitacoa " acid and polyacrylic acid. The alkali metal salts of phytic acid are also suitable ingredients.

109848 / 1IIS.

"·: *: ': .- 2Ϊ2Λ526

The polyphosphonates which can be used as a builder for the mixtures according to the invention are compounds which are exemplified as follows: I \ ^T atriuin ~ and potassium salts of ethane-i-hyaroxy-i ^ phonic acid and sodium - and potassium salts of methylene and '''A"thylcndi phosphonic acids. . ·

• ■ ·

• a ■ · * *

More examples of builders used in the satchel Invention are useful, are in U.S. Patent No. described. '. '

3. Y / hydrogen peroxide addition compounds. The hydrogen peroxide addition compounds which can be incorporated into the mixtures "according to the invention are organic and ₍ preferably inorganic.

There _- there is a great diversity of these compounds. Most of these are made by crystallization from solutions containing H _p 0 _p . Others, will by

Drying a corresponding salt and H ₂ Op containing sludge obtained. The most useful V / assers to ff pe roxide addition compounds are the perborates, see 3. the sodium.

perborate non- and tstrahydrates. Other useful perborate rates.

are the potassium and aasonium perborates with the formulas. 2KBO ₅ -H ₂ O or 22SH ^ BOv-HgO. Andsre valuable hydrogen per- ·. oxide additive compounds are the carbonate poroxyhydrates, see Sect.

B. 2UYes ₂ COv. 3HpO ₂ "and the phosphate peroxyhydrate, for example ifatoiua-." Pyropho.ophatperoxyhydrat Na ^ ₁ 1? J ^, -. 2HpO ₂ .

and cleansing cuts can be incorporated according to the invention, the urea water qtoifperoxide adai-. · Tion connection dor formula CO (IxIIp) ₂ .KpO ₂ because it is one of the addition compounds WE 'Nigon free flowing dry organic Y / ^ ater toffperoxid- ·'.

4-, shower terrain .Λ? 1υΐο1. The show regulating agents which have proven useful in the context of the invention,

- 10 -

'·' BAD ORfGiNAL

2121526

(a) Silicones. In industrial practice, the expression "Silicone" has a general meaning and includes all high molecular weight polymers, the siloxanes units and organic groups contained in which the siloxar unit -Si-O- the continuous * - che scaffolding.

Those useful in the tap of the present invention Silicones are linear or cyclic polymers of high molecular weight in which the -Si-0 unit represents continuous skeleton and wherein the organic substituents are saturated and unsaturated C - ^ .- alkyl radicals, optionally substituted by a hydroxyl group are substituted, and represent aryl radicals. Preference is given to dimethyl and methylphenyl silicones, which also polydimethyl- and polyxiethylphenylsilo-3can in which the ratio of the molecular weight of the hydrocarbon radicals to the atomic weight of the silicon atoms between 0.5 J 1 and 6 J 1, preferably between 1.8: 1 and 2.2: 1, and having a viscosity between 5 and 500,000 cSt, preferably between 200 and 25,000 cSt at 25 ° C. exhibit.

..The silicones useful in the context of this invention are, optionally, but preferably, contain other siliceous material, such as finely divided inorganic silica, for example in the form of a silica airgel. To achieve excellent viewing control results close to boiling point

. temperatures, especially with dimethyl silicones, it is highly recommended to use up to 20 wt .- #, z. B..5 "to 10 wt .- ^ j, calculated on the weight of the silicone, of silica or silicon dioxide to be added. The particle size of the silicon dioxide should not exceed du, preferably between 10 and 20 μm, and the

specific surface area more than 50 m / g gen. '

101Ii 1 / 1M «

(b) silicone-silica compounds. The silicone-silica compounds useful in the context of the invention genes consist of silicones to which finely divided inorganic silica or finely divided silicon. umaioxid is chemically bonded, which are therefore polymeric silicones, whose continuous Framework made of Silox & n units through a silicon dioxide

• particle is interrupted; an example of such connections is described in U.S. Patent No. 3,388,073.

(c) Silanated silica. In the context of the invention

). reversible silanized silica can be converted a hydrophobic silica produced by the vapor phase hydrolysis of silicon tetrachloride is, with, for example, dimethyldichlorosilane or by physically attaching the hydrophilic silica to a polysilicon, as shown in FIG U.S. Patent No. 3,207,698.

The silanated silica used in the invention must have an average particle size from 10 EU to 1, u, a degree of purity of more than

.85 % and a specific surface area greater than

t have 50 m / g. The preferred silanized silica has an average particle size between 10 and

50 mu, a specific surface area of more than

/ ο
100 m / g, with the silanized silica at a concentration of 1 Ge? /. -% in a Y / water isopropyl. alcohol-Geinisch in a ratio of 1: 1 has a pH value of more than 7. The 1st quantity of silanized silica in the detergent and cleaning agent mixture is preferably between 0.1% by weight and 1.0% by weight.

Preferred silica-containing foam control agents • are mixtures in a ratio of 3: 1 to 1: 2 parts by weight of (1) silicones, preferably dimethyl and methylphenyl silicones, in which the ratio of

109840/1886

2T24526

The molecular weight of the hydrocarbon radicals the atomic weight of the silicon atoms is between 1.8: 1 and 2.2: 1, which have a viscosity of about 1000 to 5000 cSt at 25 ° C and about 3% to 5% by weight of finely divided silica contain; and (2) silanated silica, preferably silanated silica with a medium Particle size from 10 to 25 µm and one specific Surface area of more than 200 m / g. The preferred amount of mixtures of silicones and silanated Silicic acid in the washing and cleaning agent mixtures according to the invention should be between 0.05 Wt% and 0.5 wt% vary.

(d) Particulate hydrophobic polymers and copolymers of styrene, Athens, fluoroethylene, propylene and ixobutylene with an average particle size of less than 100 μm, preferably less than 50 μm. the preferred amount of the particulate hydrophobic polymers and copolymers, the detergent and cleaning agent mixtures are incorporated according to the invention, should be between 1.5 wt .- # and 5 wt .-% vary.

5 «Polymer compounds. The polymeric compounds that ia Are useful within the scope of the invention, are polymers of a Vi-

1 1 nyl compound with the formula CHg ^B CHM, where M is a pyrrolidone (C ^ H ₆ ON) radical, a -OCOCH, -, -OCOC ₂ Hc- »radical, and copolymers thereof, with a molecular

- ¹⁵ -

2154526

weight between 5COO and 50,000; Polymers of the general formula - (CH ₂ -CH ₂ -O -) ^ with a molecular weight between 1C00 and 50,000: copolymers of maleic anhydride and a-

2 2

ner vinyl compound of the formula CH ₂ = HCM, in which M is a C ,, ^ -Alkylätherrrest or a V / hydrogen fatom, and the water-soluble salts thereof, with a molecular weight between. 10,000th and 300,000th The salts can be alkali metal, ammonium or substituted ammonium salts, preferably the sodium and potassium salts. The salt can be used in a partially or fully neutralized form. will.

The detergent and cleaning agent mixture finally obtained in accordance with the invention, small amounts of a material are grounded added, which make the product more attractive. Some examples are given below. A Anti-opacifying agents, such as benzotriazole or ethylene thiourea, can be added in amounts of up to 2% by weight. Fluorescent substances, Perfumes and dyes are for the most part not essential, but can be added in small quantities. Sodium carboxymethyl cellulose can be added in small amounts to prevent dirt from being redeposited. An alkaline one Material such as sodium or potassium carbonates or hydroxides can be used in small amounts as a supplementary pH adjuster can be added. The following can also be mentioned as suitable additives: bacteriostatics, bactericides, Enzymes, corrosion inhibitors, such as soluble alkali metal silicates, preferably ITodium silicates with a SiOp: NapO -V Ratio from 1: I. to 2.8: 1, and fabric softener.

These components of the mixtures according to the invention. are generally used in the form of complete detergent and cleaning agent batches. These complete detergent and cleaning agent formulations can be made in any of several forms, including granules, powders, flakes, tablets, and any number of approaches so long as the amounts of surfactant non-cationic agent, show suppressor and

Connection, as stated above, must be adhered to. ! In the art are numerous, tethoden known by which these "ischungen can be formed, for example, each cL can _Or ingredients are mixed in the εη given η amounts, or some of the ingredients can" be aufgeschlackt and spray dried, after which a greater Kase heat sensitive ingredients such as the hydrogen peroxide addition compounds, perfume, mixed with the spray dried ingredients, or the ingredients can be agglomerated as indicated in British Patent No. 990,252.

The effectiveness of the detergent and cleaning agent mixtures according to the invention is based on the following experiments illustrated. All blends were made by mixing the surfactant, fatty acid, builder salt, des Electrolyte and the carboxymethyl cellulose in a beater mixer, spray drying the mixture and adding the Silicones, copolymers, and perborates.

The test for evaluating the detergency, which is referred to below under the term "test", includes " a test method which is used to determine the foam profile. any, low-foaming detergent and cleaning agent approach has been developed. These tests are carried out in a specially constructed drum washing machine with a horizontally rotating drum, which is smaller than conventional washing machines and which is as accurate as possible. Movement, temperature control, detergent concentration and water conditions simulated that occur in a normal working drum washing machine. The machine is designed (with a transparent windshield) so that the foam height and water temperatures can be observed, easily measured and recorded during a special tea session. This means that the actual foam formation, if any, can be recorded , depending on the load, the detergent concentration, the dirt, the water hardness and the temperature increase can be observed.

109849/1886

Experiment A:

There were 4 rows of different detergent and cleaning agent mixtures which were composed as follows:

Components (in% by weight ) \ AB 0 D

Stearyl dimethyl oxide 10 ok 10 10 Tallow alcohol ethylene oxide
Condensate (11 oxide units
ten) 2 2 2 ■ «
2 hydrogenated fatty acids
(medium molecular weight
weight about 285) 3 3 3 3 Sodium TripolyphosOhat 32 32 32 32

3 6th , 3 6th , 3 6th , 3 6, 2 6th , 2. 6th , 2 6th , 2 1 1 1 τ.
1 - O , 22 O , 22- O , 44

Sodium perborate tetrahy- ·

drat .. 32. 32 32 32

Sodium silicate (SiO ₀ : Na ₂ O = 2: 1) f

Sodium sulfate ''

Car doxymethyl cellulose (CMC)

Silicone ¹ ^ '

Sodium salt from Malein- ' acid anhydride / vinylmethyl p%

ether copolymer '- - 11

w V / ater remainder

• ·

1) Diinethyl silicone, compounded with 3 % silica, viscosity at 25 ° C about 3000.cStj

2) Molecular weight of the copolymer in anhydride format « 250,000; · Ratio of monomers 1: 1.

4 rows of 5 aqueous solutions were prepared, each row containing ΐ% by weight of one of the mixtures A, B, O and D. The water used was tap water with a water hardness of 3.5 millimoles calcium carbonate / 1.

The washing machines 109849/1886 used for the evaluation tests

• t

κ t - ·

212 * 526

were ait cotton swab (liquid; tissue loading. '' weight ratio 8: 1) charged and with stirring ' 0.025% by weight, calculated on the aqueous washing solution, of one Mixture of oleic acid, olein and light mineral oil (ratio 1 ; 1: 1) added. · ·. ■ ·

The cotton swabs were kept in motion for 50 minutes washed (the speed of the drum was during Washing section about 50 rev / min), during which time the Water temperature increased from room temperature to boiling became.

At the end of the heating section, the cotton swabs were squeezed out, rinsed twice by hand in tap water (hardness 5.5 ΐώίοΐ calcium carbonate / 1), spun off for 10 minutes; and dried in an air dryer for 20 minutes

The washed cotton swabs were then soiled, washed, rinsed and dried and identi in the pile of a third row Shear protection, washing, rinsing and drying treatments subject.

The foam heights at the three wash sections of the five solutions of the four rows were at 40 ° C and at the boiling point recorded as follows:

Average foam size in cm: A B C D

at -40 ° C 15 7 7 5 "

at boiling point 25-10 10 .8

The three times washed rags were then with a ■ Hunter D25 color difference device using ultraviolet filters tested for whiteness (Hunter Ass. Laboratory Inc., Virginia, U.S.A.). The determined degrees of whiteness Aln Huntior L-V / erts aur, pressed, with the slightest significant difference with 95% reliability; '»-

109 849/1888

limit (LSD = 0.95) is 1 L. The mean V. degree L values the cotton swab that was washed in the five solutions were as follows:

ABCD · '■■

75 74 78, '77, ^

From these experiments it can be seen that the aqueous solutions containing 1 % of mixture A foamed extraordinarily, especially at high temperature, and that the cloths washed in solutions containing 1 % of mixture B were less foaming Whiteness LY / locally showed than those that were washed in solutions containing the same concentration of A, 0 and D, whereas the aqueous solutions containing 1% by weight of mixtures C or D, soiy that with A as well as B with regard to reduced foam profile "and V / eißgrad.L- ¥ / erten were superior. ....

Experiment B. '* *

The four series of tests, as described under test A, were repeated in a circulating drum oil washing machine, as is commonly used in Europe, under the following conditions: only 2 v / as acidic solutions were used for each mixture The cotton cloths and the artificial Sehmutz were replaced by naturally soiled T-shirts, nylon shirts, towels and polyester / cotton towels / 1j temperature: 18 ° C; exposure: 3.5 fcg i »28 1). 'Soaked, 45 minutes in fresh tap water (about 33 1)» · the 1% by weight of the mixture A, B, C or . D contained, washed, "wherein the temperature was increased from 18 ⁰ C to 92 ⁰ C, and rinsed twice with about 28 l of fresh tap water and dried.

The aqueous solution that contains 1 Gevi, -% of mixture A?

109849/1886

held foamed during the washing section at one temperature from about 40 ° C above; cleaning the various Laundry items washed in this solution were small and unusable.

The laundry items which were washed in the solutions which contained 1 % by weight of the mixtures B, C and D, respectively, were soiled again and washed twice, the degree of whiteness LV being compared with those which were obtained after knitting in a third Y / ash process ¹ . The un-

The difference in the degrees L-Y. 'locations was the same as above is indicated in connection with the cotton swabs, which with the mixtures B, C and D (experiment A) were washed.

Experiment C.

If the Stearyldimeth3 ^r laminoxid of the mixtures A, .B, 0, and D by the same percentage of sodium alkylbenzene sulfonate (C-average Atoaanzahl in the alkyl group: 11.8) replaced and the same evaluation tests with cotton cloth and artificial dirt, as described above (experiment A ), the following results are obtained:

Viewing height (in cm);

at 40 ⁰ C

at the boiling point whiteness L-values

(after the third.

Washing process) 79.8 78 79.5 79 »6

Experiment D.

If the silicone is used in mixtures A, B, C and D as well E, P, G and H with the same amount of I by a di-ethyl silicone

3 F. G H 10. 0 0 0 20th 5 5 O

replaces, which at 25 ° C has a viscosity of 200,000 cSt

so the foam heights are about the same; replaced man ee by an equal amount of a mixture in proportion

1 0 9 θ A 9/1 8 β 8

1: 1 from (a) a Diine thy Isilikon, which is co-compounded with 3 wt .-% of a silica, which has a viscosity of 3000 · cSt at 25 ° C, and (b) a silanized silica n with an average particle size of about 15 9 ^, and a specific surface area of about 215 m / ß> ^as is the foam to about 50% (for B, 0, and D) is reduced or disappears almost completely, even in the 'boiling temperature (at F and G), while in all experiments the C / E L values were the same as indicated above for the corresponding mixtures (experiments A and C). ·

Try.

Replacing the 0.025 wt .-% of the group consisting of oleic acid, olein and light mineral oil soil (experiment A) by the same l £ close a mixture of 8 parts of dirt from air conditioning filters (35% inorganic material, mostly ash; 59 ⁰ A different organic Compounds, e.g. lipids; 6 % moisture) and 2 parts of a mixture of oleic acid, oleic and light mineral oil (ratio 1: 1: 1), of which a slurry has been made by dispersing this mixture in tap water using a high speed stirrer , and repeats the four legs of five tests with cotton swabs as described for mixtures A, B, 0 and D above (test A), the foam heights and the differences in the whiteness L values are the same.

Attempt F.

Another series of five attempts was made, as in the case of « Experiment A 'described, carried out, but the following mixtures indicated in the table were used. · The excellent foam suppression and is shown again Maintaining the whiteness of the mixtures J, L, Nj P, R, T and V prepared in accordance with the present invention are.

Tab .: »/. , 108849/1886

Tabel :

Ingredients (in wt .- #): I. J K L. φ M. 6.5 0 P. Q R. S. T U V V.
I. 7th (Sodium salt) 6.5 6.5 10 10 6.5 5.6 10. 10 10 '10 2 Tallow alcohol sulfate (sodium
uia salt) 5.6 5.6 - - ' 2 5.6 - • - - - - - - - 3 5- (C .; ß-alkyldimethyl-
acuaoni ο) -2-hydroxypr op-
an-1-sulfonate (sodium
salt) I. 5 7th 7th 5- (C ^ /. O-alkyldimethyl-
ammonio) -propane-1-sul-
fonat (sodium salt) -52 - 7th • a » Tallow alcohol / ethylene oxide
(11) condensate _ 2 * «SB _ 4th 2 2 2 2 2 2 2 hydrogenated fatty acid (med
ler molecular weight "
285) 4th 4th 5 4th 52 I.
5 5 3 3 3 3 3 Sodium tripolyphosphate 52 32 52 52 - - - - 32 32 32 Trisodium nitrilotr
acetate 24 24 • _-

Continued tab .; IO B. ■ Components (in wt .- $ £): I. J 1 5 E. L. « . VfI IE N , 3 O P. - 32 3 Q R. . 32 S. T 3 - U V Trinatr iumethylene-1 -hydr- 2 , 2 2 2 44 • 5
«« ^ oxy-1,1-diphosphonate - - Zl - -. - - - - 3 δ, 18th 18th , 3. 6.3. - - - - m> Soda pera rat trahy- ,1' 2 14 20th m
m drat 32 32 32 52 32 32 32 1 32 1 32 32 32 32 Sodium silicate (SiO ₂ / 2 * »11 44 O, , 22 0.22 Na ₂ O - 2.0) β 6th 6, 3 6, 6, J 6 6, 6th 6th , 3 6, 6.3 6.3 Sodium sulfate 8th, 5 7, 7, 2 G, 7, 2 6 15, 21st 1 , 2 6, 7 * 2 6 ^ 2 Carboxymethyl cellulose 1 1 1 "1 1 1 1 1 1 1 1 Silicone (see mixture A) O, 22 O ₁ Μ » - 11 O 0, 44 O 0, 0.22 0.22 silanized silica . 1 1 (mean particle size:
about 15 mu *, more specific
Surface area: approx ·. ο, 22 O ₁ 0, 11 O ■ Lineal anhydride / vinyl methyl ether copolymer (β. Mixture A) 1 1 1 •

Continued table: I J K L II N * *
0 0
5 5
78.3 79.8 15th 15th
O 0.
78.3 79.5 0 0
2 .2
78.3 79.8 0 p Q H S Φ U V OO
6 O
78 80 12 O
30 5
76 77.8 % 5
10. 9
75 78. Components (in% by weight): 1
* OQ + * • - - Vinyl pyrrolidine / vinylace
tat-Copoiyner (sodium salt '
(Mole weight: about 25,000]
water Foam Heights (Avg
section of 15)
at 40 ⁰ O
• at the boiling point
Whiteness L values
(after 3 washes
corridors) OO
OO
77.7 79.1

9 *

The following examples serve to illustrate but not the limitation of the new mixtures according to the invention. All percentages in the examples relate based on% by weight.

Example 1: A free-flowing, finely divided detergent and cleaning agent mixture is prepared by slurrying in a cross beater mixer, the surface-active agents, builders, electrolytes, carboxymethylcellulose, brighteners and water, spray-drying the slurry, the sodium perborate, copolymer and schaumregelnde means having L · the spray dried Grains dry mixed and the perfume is sprayed onto the agglomerates in a very fine distribution. The end product consists of: '. ■ """'.

9.30 % sodium salt of linear alkyl benzene sulfonate

(average molecular weight of the alkylbenzenes 241), · · - '

$ 26.10 sodium tripolyphosphate,
■ 3.40 % hydrogenated fatty acid (average molecular weight

• 285), ".". '. · 3J40 % condensation product. Tallow alcohol and 11 moles of ethylene oxide per mole of alcohol, -. '. '6.20% sodium silicate (Si0 ₂ / Na ₂ 0 »2.1),'. "·. · 0.80 '$ carboxymethyl cellulose,

0.40 % toluenesulfonate sodium salt,

1.50% sodium salt of maleic anhydride / vinyl methyl ether copolymer (molecular weight about 200,000, monomer ratio 1: 1), 0.20 % dimethyl silicone (viscosity: 200,000 cSt at

13.00 % sodium sulfate,

25.00. % Sodium porborate tetrahydrate,

2.10 ° / o brightener, perfume,

8.60 % moisture.

1O984Ö / 108I

An aqueous solution (tap water) containing 1 % of ^{this mixture produces only reduced foam at temperatures between room temperature and ^ 2 0} when used in a washing machine of the reverse type or in a conventional (tub) automatic washing machine that can be loaded from above G and cleans thoroughly.

Other suitable mixtures are: Example 2:

9,00 ° / o Laurylphosphinoxid, 25.00% sodium tripolyphosphate,

2.00 % sodium ethylenediamine tetraacetate, 1.00 % carboxymethyl cellulose,

5.60 % sodium toluenesulfonate, 27.00% sodium sulfate, 17.50% sodium perborate tetrahydrate, 2.00 % sodium chloride,

Λ ^ 0% styrene maleic anhydride copolymer (monomer

ratio 1: 1; Molecular weight: about 50,000),

0.45 ° / o silanated silica (average particle size: about 20 mu; specific surface area about 180 ι a'7g)

1.00 ° / o enzyme product (40% active protease), 2.55% Miscellaneous, 7.50% moisture.

The copolymer can be replaced by the sodium salt of maleic anhydride / ethylene copolymer (molar weight: 15Ο.ΟΟΟ) or by the ethanolamide derivative of maleir _: acid anhydride / vinyl ethyl ether copolymer (ilol weight: 25,000).

Example?: · "

j 00 ' ^c / o sodium coconut alcohol sulfate, 25.00% sodium tripolyphosphate, 4.00% sodium nitrilotriacotate,

109 8 4 9/1886

- 2124576

21.00 % sodium sulphate,

1.50 ° / o Enzyniprodukte (40% active SnzymgeniiEch containing 8 parts of protease and 2 ropes Aaylase)

3.60 % sodium toluene sulfonate,

4.00 % sodium silicate (SiO ₂ ZSTa ₂ O = 1.6: 1), 2.50 % sodium salt of LIaIe in the acid hydri d / vinyl line thy 1 ethyl copoly & er (monomer ratio 2: 1; molar weight: 75,000) , ^: .

0.80 % Llethylphenylsilikon, coiapoundiort with 2.5% by weight - silica (viscosity at 25 ⁰ C: about 150,000 cSt),

2.60 % miscellaneous (perfume, brightener, dye),

8.00 % moisture.

Example "4-:

7.00 % K "atriuii-3- (Si, N-diiaethyl-H-tetrc! .Decylaiamonio) -

propane-1-phosphate,. .

AO, 00 % iiatriuratripolyphosphate, ''

27 »50 % catriur perborate tetrahydrate, 9.50 % liatriuiiaulphate,

4.50% sodium salt of maleic anhydride / vinyl methyl ether copolymer (Mono ratio 1: 1; molar weight: 50,000), -

0, ^ 0 % silanized silica (particle size: 15

specific otier area c j 215 ux / g),

9.70 % sodium silicate (SiO ₂ ATa ₂ O = 1.6: I) ₁ . Rest moisture, perfume.

Example · .5! '

17.50 % sodium linear alkyl beiizolsulfonate (G ** η),

40.50 % sodium tripolyphosphate,

4.00 % sodium nitrilotriacetate,

2.00 % Natriuraethylene-1-hydro: cy-1,1-diphosphonate,

0.50 ° / o monoethanolamine,

0.50 % ethylphosphonyl silicone (viscosity: 200,000 cSt at 25 ° C),

109849/18 8 6

- 26 -

• - 2174 * 26-

• Tr

2.50 % sodium al ζ of potassium anhydride / vinylniethyl copolymer (egg ratio 2: 3; molar weight: 225,000),

6.00 % sodium silicate (Si0 ₂ / Na ₂ 0 »1.6: 1),

2.00% sodium toluenesulfonate, 12.00% sodium sulfate,

3.20 % miscellaneous (minor components),

9.50 % moisture.

Example6:

9.50% sodium tallow alcohol sulfate,

7.80 % sodium linear alkylbenzenesulfonate (C ^ ^ c) »

2.10 % diethanolamide,

49.00 % sodium tripolyphosphate,

5.90 ° / o sodium silicate (F> i0 ₂ / Na ₂ 0 = 1.8: 1),

12.70 % sodium sulfate,

4.00% - / = CH ₂ -CH (-OCOCH.) _ 7-polymer (molar weight: 20,000), '

'' 1.50 % polyethylene glycol (molar weight: 20,000),

6.50 % moisture.

B ei s ρ i e 1 7:

5.00 % tallow alcohol / ethylene oxide (11) condensate,
45.00 % sodium tripolyphosphate,
16.00 % chlorinated trisodium phosphate,
20.00 % sodium silicate (Si0 ₂ / Na ₂ 0 = -2.8: 1),
1.50 % sodium salt of maleic anhydride / vinyl butyl ether copolymer (monomer ratio 1: 1; molar weight: 150,000),
2.00 % sodium salt of vinylpyrrolidone / vinyl acetate-Co-

polymer (onomerverhältnis 1:!.! 1 × Mol-Gew.50.OOO), 0.50% of a 1: 1 mixture of Dinethylsilikon (viscosity: 200,000 cSt at 25 ⁰ C) and silanized silica (average particle size: 15 ρ ; socially

p " 7
see surface 215 κVg; pH in 1:. 1 mixture of

V / ater / isopropyl alcohol: 8.59), 8.00 % moisture.

Claims (8)

Patent claims: Detergent and cleaning agent mixture containing a surface-active agent, a schaumregelndes agent and optionally a builder salt, a bleaching agent, and other conventional detersive adjuncts, characterized in that, calculated on the basis of a finished product, about 2 to about 30 wt -.% Of a water soluble organic, non-cationic surfactant? . 0 to about 80 wt -%, preferably about 15 weight -% to 45 wt .- $, a water-soluble builder salt. about 0.05 to about 5 percent by weight of a silicone, a finely divided silanized silica, finely divided hydrophobic polymers and copolymers of styrene, Athens, fluorethylene, butylene and isobutylene, and mixtures thereof as foam regulating agents; and about 0.5 to about 8.0% by weight of polymers of a vinyl compound of the formula CH ₂ = HCM, where M is a pyrrolidone, -OCOCH, -, -OCOC ₂ Hc-, -OCH, -, -OC ₂ H ₁₅ -ReSt and their copolymers, with a molecular weight between 1000 and 50,000; Polymers 4 of the general formula - (CHp-CH ₂ -O) - with a molecular weight between 1000 »And 50,000; Copolymers of maleic anhydride and a 22 vinyl compound of the formula CH ₂ = HCM, where M is a C ^ h -alkyl ether radical, a phenyl radical or a hydrogen atom, with a molecular weight between 10,000 and 300,000, or their water-soluble alkali metal, ammonium and substituted ammonium salts contains. 109849/1886 2. Washing and cleaning agent mixture according to claim 1, characterized in that it comprises about 7 to about 14 wt -.% Water-soluble alkali metal salts of an organic sulfur "äu- Reaction product contains which in its molecular structure contains an alkyl radical with 8 to 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical. 3. washing and Mnigungsmittelmischung according to claim 1, characterized in that it comprises about 15 Gev .-% to about 80 wt -.%, Preferably about 15 wt -.% To about 45 parts by weight of Si, a water-soluble inorganic builder salt, barren Mixtures thereof, alone or in combination with a water-soluble organic builder salt, or mixtures thereof. 4. washing and cleaning agent composition according to claim 1, characterized in that it comprises about 10 weight JS to about 30 wt -.% Of a water-soluble organic builder salt, or mixtures thereof. 5. detergent mixture according to claim 1, characterized in that it contains about 12 wt. Ί to about 50 wt. preferably about 25 weight percent to about 35 weight percent, a hydrogen peroxide addition compound, preferably sodium perborate tetrahydrate. 6. detergent and cleaning agent mixture according to claim 1, characterized in that it contains about 0.05 wt. % To about 3.0 wt. a Di-CL ^ -alkyMlikons, preferably contains dimethylsilicone or methylphenylsilicone, the ratio of the molecular weight of the hydrocarbon radicals to the atomic weight of the silicon atoms between 0.5: 1 and 6: 1, preferably between 1.8: 1 and 2.2: 1, fluctuates, and the silicone has a viscosity between 5 and 500,000 cSt, preferably between 200 and 25,000 cSt, at 25 ° Ο. to have. 109849/1886 7 1? Λ R 2 6 30th 7. detergent mixture according to claim 6, characterized in that the silicones 3 Gow .-% to 10 Gow.- ° / o _% calculated on the weight of the silicones, SiIisiuadioxid with a mean particle size of at most 25 JyU and one
specific surface area of more than 50 m / g. 8. Detergent and cleaning agent mixture according to claim 1, characterized in that it contains 0.1% by weight to about 1.0 % by weight of silanized silica with an average particle size
contains from 10 rough to 1, u and a specific surface area of more than 50 m ² / g. 9 »Detergent and cleaning agent mixture according to claim 1, characterized in that it is about 0.5% by weight to about 5% by weight
% By weight, preferably about 1.0% by weight to about 2.5% by weight, of a maleic anhydride / vinyl ~ C ^ _ ^ - alkyl ether - copolymer,
preferably a maleic anhydride / vinylraethyl ether, and the alkali metal salts thereof with a molecular weight between 10,000 and 300,000, preferably between 75,000 and
200,000. ·· -. '" For: Procter & Gamble European Technical Center ■ Lawyer 109849/1886 - 30 -